Analysis of Polychlorinated Biphenyl (PCB) Residues in Stream Sediment Samples Collected September 9, 1999 from the Bayou Creek System

Transcription

1 Analysis of Polychlorinated Biphenyl (PCB) Residues in Stream Sediment Samples Collected September 9, 1999 from the Bayou Creek System Wesley J. Birge David J. Price DRAFT REPORT March 14, 2000 Submitted to Jon Maybriar Division of Waste Management Kentucky Department for Environmental Protection

2 INTRODUCTION Stream sediment samples were collected for PCB analyses from Big and Little Bayou Creeks on September 9, This report includes 41 samples analyzed for PCBs of which 9 were duplicate assays (i.e. BB1A, BB1, BB3, BB7, LB2A, LB2A, LB2, LB3, LB4). There were also 31 QA samples. Sampling stations BB1 through BB9 on Big Bayou Creek (26 samples) and LB2A through LB4 on Little Bayou Creek (13 samples) were included in this field survey (Figure 1; Tables 1, 2). Two samples at the new reference station, upstream of BB1 and designated BB1A, also were collected. In addition, Massac Creek (MC) was sampled and served as a reference station independent of the Bayou Creek system. A minimum of two samples were collected for PCB assays from each of the sampling stations. Three Aroclors (i.e. 1248, 1254, and 1260) were determined for each sample. With respect to Little Bayou Creek, an additional 16 dried sediment samples, including 6 duplicates, were analyzed for PCBs in the clay/silt fractions (Table 3). METHODS Sediment Collection Sediment samples were restricted to the upper 5-10 cm of sediment soil, including depositional areas when found. All sediment samples were collected in acetone-rinsed 0.47 L glass jars with teflon or aluminum foil-lined lids. Stainless steel spoons and scoops used for collections were acetone-rinsed between sampling stations. Sediment Extraction 1

3 Wet sediment extractions of PCBs were performed following U.S EPA SW-846 Method 3540C for Soxhlet extraction (U.S. EPA, 1997; Erickson 1997). All solvents used were pesticide grade and were screened for organic contaminants prior to use. Weighed sub-samples (average wet weight g; average dry weight g) were extracted with 300 ml of acetone/methylene chloride (1:1 v:v) in a 500-mL Soxhlet extractor for 15 h. The extract was concentrated to near dryness in a Roto-evaporator (Buchi Model RE121). The reconstituted samples (5.0 ml in iso-octane) were cleaned of interferences as described below and then analyzed by gas chromatography. The dry clay/silt fractions from Little Bayou Creek sediments were also analyzed. The sediment sample was air-dried for 7d and sieved (past 180-µm mesh) to obtain the clay/silt fraction. This fraction was then extracted as described above. All sieves and trays were stainless-steel and solvent cleaned between samples. Sample Cleanup Lipid and pesticide cleanup was performed by eluting a 2.0 ml sample through a micro-column of 2.0 g activated mesh Florisil (100 o C/24 h) with 10.0 ml hexane and evaporated to 2.0 ml (Erickson, 1997; U.S EPA, 1997 Method 3620B). Elemental sulfur was removed by shaking 2-propanol (2 ml) and tetrabutylammonium sulfite (2 ml), adding ultra-pure water (8 ml) and reshaking. The organic extract was removed and mixed with 2.0 ml concentrated sulfuric acid (Jensen et al., 1977; U.S EPA, 1997 Method 3660B). A 4 µl sub-sample was analyzed by gas chromatography. 2

4 Analysis by Gas Chromatography Samples were analyzed for Aroclors 1248, 1254, and 1260 according to SW-846 Method 8082 using gas chromatography (U.S. EPA, 1997). Analysis was performed using a Hewlett-Packard (HP) Model 5890A gas chromatograph equipped with an electron capture detector and an HP Model 7673A Automatic Sampler. Samples were analyzed using a 60 m x 0.53 mm ID SPB-5 (0.5-µm film) fused silica megabore column (Supelco, Inc.) with ultra-high purity helium and nitrogen as carrier and makeup gases, respectively. Temperature program: 160 o C (6 min) ramp at 10 o C/min to 235 o C (0 min) ramp at 0.9 o C/min to 260 o C (10 min); Injector temperature, 280 o C; Detector temperature, 300 o C. PCB peak heights were quantified using an HP Model 3396A integrator and multiple-peak linear regression analysis was performed with Lotus-123 software. Aroclor levels were calculated from heights of 6 to 9 peaks for Aroclor 1248, and 4-6 peaks for Aroclors 1254 and Five external standards were used for calibration curves and for every tenth sample either a solvent blank or a standard was analyzed. The Lotus program regresses data from PCB standards to the sample being analyzed. Each peak selected for each Aroclor class is statistically analyzed (e.g. standard deviation; standard error; relative deviation). Unless the specified number of acceptable peaks per Aroclor were obtained, the sample was reanalyzed. This included further cleanup for pesticides or sulfur as indicated, as well as a new standard curve. Chromatographs and bench records for all PCB assays will be maintained as given below under quality assurance. 3

5 Quality Assurance Permanent bench records were kept of all assays and annotated as required under Good Laboratory Practices (Federal Register, 40 CFR, Part 160, August 17, 1989). All printouts and graphic recordings were filed and are open for inspection. These bench records will be archived within two years after the close of the project but retrievable upon request. Chain of Custody were maintained for all samples collected. Quality assurance included 1) assays for certified and prepared standards, 2) duplicate assays, 3) recoveries, and 5) glassware solvent blanks. Nine stations were analyzed in duplicate by taking and weighing an additional sub-sample from the same jar. These duplicates were prepared and analyzed as a regular sample. RESULTS Results for PCB analyses of Big Bayou sediments are given in Table 1. Although PCBs were detected at BB3, BB4, BB7, BB8, and BB9, all values were below the minimum quantitation limit (i.e. lowest standard). The analysis of wet sediment samples revealed little or no detectable PCB contamination (Table 1). For the next sampling interval, sediment assays for Big Bayou Creek will be based on the clay/silt fraction and greater attention will be given to stations BB3 through BB7. The analysis of wet sediments collected from Little Bayou Creek revealed detectable concentrations of PCB at all stations (i.e. LB2A, LB2, LB3, LB4). However, the values were below µg/g. The higher values were observed at LB2A which is 4

6 situated downstream of effluent 011. To obtain more analytical precision, 16 sediment samples from Little Bayou Creek were dried and sieved prior to the analysis of the clay/silt fractions (Table 3). The resulting concentrations were higher by about one order of magnitude. As before, the higher concentrations were found at station LB2A. These ranged from to µg/g for Aroclor 1248 and to µg/g for Aroclor Values for the three Aroclor were totaled for each sample and the results are given in Table 3. Total PCB concentrations in µg/g ranged from to at LB2A; to at LB2; to at LB3; and to at LB4. The major source of PCB contamination likely is effluent 011. It should be noted that water samples collected in September 1999 and October 1998 from BB2A and BB2 contained detectable concentrations of PCBs (Birge and Price, 1999a, 1999b). The occurrences constituted violations of the State of Kentucky PCB water quality standard. Additional sampling should be conducted on Little Bayou Creek, including all effluent ditches. There is no official standard for PCB sediment contamination. However, numerous credible sources place the limit at or below 0.10 mg/kg (ppm). A listing of these sources is appended at the end of this report. Results of quality assurance assays are given in Tables A1 through A5. Confirmatory analysis of sediment samples were conducted on wet sediments using a second GC unit. The results given in tables A1 and A2 are similar to those given in Table 1 and Table 2. All control assays were negative (Table 3). Percent PCB recoveries varied from 99% to 117% for the regular sample series (Table A4) and 81% to 104% for the confirmatory series. 5

7 REFERENCES Birge, W.J. and D.J. Price. 1999a. Analysis of Metals and Polychlorinated Biphenyl (PCB) Residues in Water Samples Collected September 9, 1999 from the Bayou Creek System. DRAFT REPORT, December 3, Submitted to Jon Maybriar, Division of Waste Management. Birge, W.J. and D.J. Price. 1999b. Report to FFOU on Metals, Mercury and Polychlorinated Biphenyl (PCB) Residues in Water Samples Collected October 20, 1998 from the Bayou Creek System. DRAFT REPORT, January 26, Submitted to Jon Maybriar, Division of Waste Management. Erickson, M.D Analytical Chemistry of PCBs, 2 nd Raton, FL. pp.667. edition. CRC Press, Boca Federal Register Good Laboratory Practice Standards. 40 CFR Part 160. August 17, Washington, DC. Jensen, S., Renberg, L., Reutergådh, L Residue analysis of sediment and sewage sludge for organochlorines in the presence of elemental sulfur. Anal Chem. 49(2): U.S. EPA Test methods for evaluating solid wastes, SW-846, Final Update 3. Office of Solid Waste and Emergency Response, Washington, DC. 6

8 Table 1. PCB results for PGDP stream sediment samples collected from Big Bayou Creek September 9, Sample Aroclor Conc. (µg/g) Station Wet Wt. Dry Wt. % Name Date Sample a Duplicate b (g) (g) Moisture MC c 09/09/99 PSED1 A <0.003 <0.003 <0.003 MC 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB1A 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB1A 09/09/99 PSED1 B <0.002 <0.002 <0.002 BB1A 09/09/99 PSED2 A <0.004 <0.004 <0.004 BB1 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB1 09/09/99 PSED1 B <0.003 <0.003 <0.003 BB1 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB2 09/09/99 PSED1 A <0.004 <0.004 <0.004 BB2 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB2A 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB2A 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB3 09/09/99 PSED1 A <0.003 <0.003 BB3 09/09/99 PSED1 B <0.003 <0.003 <0.003 BB3 09/09/99 PSED2 A * <0.003 <0.003 BB4 09/09/99 PSED1 A * <0.003 <0.003 BB4 09/09/99 PSED2 A <0.005 <0.005 <0.005 a PSED1 and PSED2 are two samples collected separately. b Duplicates A and B were taken from the same sample. c MC identifies Massac Creek, a control stream independent of the Bayou Creek system. * PCBs detected, however value below Minimum Quantitation Limit (MQL). 8

9 Table 1,Continued. PCB results for PGDP stream sediment samples collected from Big Bayou Creek September 9, Sample Aroclor Conc. (µg/g) Station Wet Wt. Dry Wt. % Name Date Sample a Duplicate b (g) (g) Moisture BB5 09/09/99 PSED1 A <0.004 <0.004 <0.004 BB5 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB6 09/09/99 PSED1 A <0.005 <0.005 <0.005 BB6 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB7 09/09/99 PSED1 A < * 0.002* BB7 09/09/99 PSED1 B <0.003 <0.003 <0.003 BB7 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB8 09/09/99 PSED1 A * <0.003 <0.003 BB8 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB9 09/09/99 PSED1 A <0.004 <0.004 <0.004 BB9 09/09/99 PSED2 A < * 0.002* a PSED1 and PSED2 are two samples collected separately. b Duplicates A and B were taken from the same sample. c MC identifies Massac Creek, a control stream independent of the Bayou Creek system. * PCBs detected, however value below Minimum Quantitation Limit (MQL). 9

10 Table 2. PCB results for PGDP stream sediment samples collected from Little Bayou Creek September 9, Sample Aroclor Conc. (µg/g) Station Wet Wt. Dry Wt. % Name Date Sample a Duplicate b (g) (g) Moisture LB2A 09/09/99 PSED1 A < * LB2A 09/09/99 PSED1 B < LB2A 09/09/99 PSED2 A < LB2A 09/09/99 PSED2 B < LB2 09/09/99 PSED1 A * < * LB2 09/09/99 PSED2 A * < * LB2 09/09/99 PSED2 B < * LB3 09/09/99 PSED1 A < * LB3 09/09/99 PSED2 A < * LB3 09/09/99 PSED2 B < * LB4 09/09/99 PSED1 A < LB4 09/09/99 PSED2 A < LB4 09/09/99 PSED2 B < a PSED1 and PSED2 are two samples collected separately. b Duplicates A and B were taken from the same sample. * PCBs detected, however value below Minimum Quantitation Limit (MQL). 10

11 Table 3. PCB results for the clay/silt fraction of PGDP stream sediments collected from Big Bayou Creek September 9, Sample Aroclor Conc. (µg/g) Station Dry Wt. Name Date Sample a Duplicate b (g) Total LB2A 09/09/99 S1 A LB2A 09/09/99 S2 A LB2A 09/09/99 S2 B LB2 09/09/99 S1 A LB2 09/09/99 S1 B LB2 09/09/99 S2 A LB2 09/09/99 S2 B LB2 09/09/99 S1 A LB2 09/09/99 S1 B LB2 09/09/99 S2 A LB2 09/09/99 S2 B LB3 09/09/99 S1 A LB3 09/09/99 S2 A LB4 09/09/99 S1 A LB4 09/09/99 S2 A LB4 09/09/99 S2 B a S1 and S2 are two samples collected separately. b Duplicates A and B were taken from the same sample jar. 11

12 Figure 1. Location of Monitoring Stations and Continuously Flowing Effluents on Big and Little Bayou Creeks BB9 OHIO RIVER Big Bayou Creek BB5 006 BB4 BB4A BB3 BB2 BB2A BB8 BB7 BB CF1 (Not to Scale) PGDP CF CF3 Little Bayou Creek LB4 LB2 LB2A LB3 BB1 BB1 to BB8 6.1 km BB8 to Ohio River 7.4 km LB1 12

13 Table A1. Confirmatory PCB results for PGDP stream sediment samples collected from Big Bayou Creek September 9, Sample Aroclor Conc. (µg/g) Station Wet Wt. Dry Wt. % Name Date Sample a Duplicate b (g) (g) Moisture MC c 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB1A 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB1 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB2A 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB3 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB4 09/09/99 PSED1 A <0.003 <0.003 <0.003 BB5 09/09/99 PSED1 A <0.004 <0.004 <0.004 BB6 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB7 09/09/99 PSED2 A <0.003 <0.003 <0.003 BB9 09/09/99 PSED1 A <0.004 <0.004 <0.004 a PSED1 and PSED2 are two samples collected separately. b Duplicates A and B were taken from the same sample. c MC identifies Massac Creek, a control stream independent of the Bayou Creek system. 13

14 Table A2. Confirmatory PCB results for PGDP stream sediment samples collected from Little Bayou Creek September 9, Sample Aroclor Conc. (µg/g) Station Wet Wt. Dry Wt. % Name Date Sample a Duplicate b (g) (g) Moisture LB2A 09/09/99 PSED2 B < LB2 09/09/99 PSED2 B < * LB3 09/09/99 PSED2 B < LB4 09/09/99 PSED2 B < a PSED1 and PSED2 are two samples collected separately. b Duplicates A and B were taken from the same sample. * PCBs detected, however value below Minimum Quantitation Limit (MQL). 14

15 Table A3. PCB concentrations in controls a for stream sediment samples from Bayou Creek System collected September 9, Aroclor Conc. (µg/ml) b Sample Name CON PCON1SED <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 CON PCON2SED <0.001 <0.001 <0.001 CON PCON3SED <0.001 <0.001 <0.001 CON PCON4SED <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 CON PCON5SED <0.001 <0.001 <0.001 a Glassware, solvent and extraction thimbles extracted as a regular sample. b Second number corresponds to confirmatory analysis on separate GC. 15

16 Table A4. PCB concentrations in procedure recoveries a for stream sediment samples from Bayou Creek System collected September 9, Aroclor Conc. (µg) µg Expected Measured Percent Sample Name Aroclor Spike Conc. Conc. Recovery RECO PPRR RECO PPRR RECO PPRR RECO PPRR RECO PPRR RECO PPRR a 300 ml of solvent were spiked with the respective Aroclor, extracted and analyzed as a regular sample. 16

17 Table A5. Confirmatory PCB concentrations in procedure recoveries a for stream sediment samples from Bayou Creek System collected September 9, Aroclor Conc. (µg) µg Expected Measured Percent Sample Name Aroclor Spike Conc. Conc. Recovery RECO PPRR RECO PPRR RECO PPRR RECO PPRR RECO PPRR RECO PPRR a 300 ml of solvent were spiked with the respective Aroclor, extracted and analyzed as a regular sample. 17

18 Summary of Sediment Criteria for PCBs 0.1 mg/kg -Based on U.S. EPA (1990) sediment cleanup level of 1.0 mg/kg for 10-5 risk, adjusted for 10-6 cancer risk (risk assessment by Dr. Albert Westerman) -Ruling by Judge W.L. Graham. March 27, Commonwealth of Kentucky. Franklin Court. Civil Action No. 86-CI Division II. Frankfort, KY. Circuit mg/kg -sediment threshold limits -based on equilibrium partitioning corrected for 2% organic carbon -S.P. Pavlou The Use of the Equilibrium Partitioning Approach in Determining Safe Levels of Contaminants in Marine Sediments. In: Fate and Effects of Sediment-Bound Chemicals in Aquatic Systems. K.L. Dickson, A.W. Maki, and W.A. Brungs, eds. Pergamon Press, Elmsford, NY. pp <0.13 mg/kg -sediment concentrations at or above may adversely effect aquatic life -Chapman, P.M., R.C. Barrick, J.M. Neff, and R.C. Schwartz Four Independent Approaches to Developing Sediment Quality Criteria Yield Similar Values for Model Contaminants. Journal of Environmental Toxicology and Chemistry 6: mg/kg -based on equilibrium partitioning, corrected for 4% organic carbon -U.S. EPA National Perspective on Sediment Quality. Washington, DC. 84 pp. <10 µg/kg NON-ELEVATED >20 µg/kg SLIGHTLY ELEVATED >50 µg/kg ELEVATED >200 µg/kg HIGHLY ELEVATED >1500 µg/kg EXTREME -based on total PCBs direct analysis of sediments throughout the State of Illinois; tiered classification system based on standard deviations from background mean (<10 µg/kg). -Kelly, M.H. and R.L. Hite Evaluation of Illinois Stream Sediment Data IEPA/WPC/ Illinois Environmental Protection Agency. Springfield, IL. 100 pp mg/kg TOTAL NO EFFECT 0.07 mg/kg TOTAL LOWEST EFFECT, 10.6 mg/kg SEVERE EFFECT mg/kg 1016 LOWEST EFFECT, 1.06 mg/kg SEVERE EFFECT 0.03 mg/kg 1248 LOWEST EFFECT, 3.0 mg/kg SEVERE EFFECT 0.06 mg/kg 1254 LOWEST EFFECT, 0.68 mg/kg SEVERE EFFECT mg/kg 1260 LOWEST EFFECT, 0.48 mg/kg SEVERE EFFECT -based on screening method, corrected for 2% organic carbon 18

19 -Persaud et al (Draft). The Provincial Sediment Quality Guidelines. Water Resources Branch, Ontario Ministry of the Environment. Ottowa, Ontario, Canada mg/kg TOTAL mg/kg mg/kg mg/kg based on screening method, corrected for 2% organic carbon -Hart, D.R. et al Development of Sediment Quality Guidelines. Phase II - Guidelines Development. Beak Consultants, Ltd. Brampton, Ontario, Canada mg/kg TOTAL -based on background method -Sullivan, J. et al Report on the Technical Subcommittee on Determination of Dredge Material Suitability for In-Water Disposal. Wisconsin Department of Natural Resources. Madison, WI. -Scheuttepelz, D. January 9, Revised January 16, Memo to Mark Giesfeldt: Development of Sediment Quality Criteria for the Litttle Menomonee River/Moss American Superfund Site. Wisconsin Department of Natural Resources. Madison, WI mg/kg TOTAL -Based on screening method, corrected for 2% organic carbon for saltwater sediments -Neff, J.M. et al Final Report- Sediment Quality Criteria Methodology Validation: Calculation of Screening Level Concentrations from Field Data. Battelle, Washington, DC mg/kg based on equilibrium partitioning, corrected for 2% organic carbon -U.S. EPA Interim Sediment Criteria Values for Nonpolar Hydrophobic Organic Contaminants. SCD 17. Washington, DC. 36 pp mg/kg TOTAL OPEN WATER <2.0 mg/kg TOTAL UNRESTRICTED LAND >2.0 mg/kg TOTAL RESTRICTED LAND -method(s) unavailable, disposal of dredged sediments -Anonymous Guidelines for the Management of Dredged Material. Ontario Ministry of the Environment. Toronto, Ontario, Canada. 19